Crosslinking cotton with haloalkyl phosphine oxides



- phosphine oxide,

United States Patent Int. Cl. D06m 13/28 US. Cl. 8120 26 Claims ABSTRACTOF THE DISCLOSURE Improved wet wrinkle recovery is obtained bycrosslinking cotton in the presence of a base with certain bisandtris(ha1oalky1)phosphine oxides.

A nonexclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This invention relates to certain organophosphorus compounds useful astextile finishing agents. Specifically, this invention relates tohaloalkyl phosphine oxides. More specifically, this invention relates toa process for crosslinking cellulosic textiles with bisandtris(haloalkyl) phosphine oxides to impart to the finished products Wetwrinkle resistance.

Inventors know of no prior art which would teach the treatment oftextiles by any similar process. Details of the work which led to theunexpected discovery of the instant invention have been disclosed bythese inventors in their crosslinking Cotton with HalomethylphosphineOxides, which paper appears in the American Dyestufi Reporter 56(17),page 614 (1967).

The principal object of the instant invention is to provide a processfor crosslinking fibrous cellulosic textiles.

A further object of the instant invention is to provide a process forproducing fibrous cellulosic textiles with an improved wet wrinklerecovery quality.

In the inventigative work which led to the instant invention it has beenfound that phosphine oxides of the graphic formula where X is a halogen,will react with cellulosic hydroxyl groups in the presence of alkalinecatalysts to crosslink cellulose. It has also been found that phosphineoxides of the graphic formula where X is a halogen, will react withcellulosic hydroxyl groups in the presence of alkaline catalysts tocrosslink cellulose.

Compounds which are useful reagents in practicing the invention includetris(chloromethyDphosphine oxide, tris(bromomethyl)phosphine oxide,tris(iodomethyl) methyl bis(chloromethyl)phosphine oxide, methylbis(bromomethyl)phosphine oxide, methyl bis(iodomethyl)phosphine oxide,and the like.

The reaction of the reagents of the invention, above, with cellulosicmaterials takes place between the cellulosic hydroxyl groups and thehalogen atoms of the phosphine 3,535,073 Patented Oct. 20, 1970 oxides,thereby crosslinking the cellulose through stable ether linkages.Cellulose crosslinking is proven by insolubility of the products of thereaction, which are cellulosic derivatives, in a standard 0.5 molarcupriethylenediamine hydroxide aqueous solutiona common cellulosesolvent.

Cotton fibers, regenerated cellulose, and other natural cellulosicfibers can be employed in reducing the invention to practice;nevertheless, the preferred application would be on cotton fabrics.

The tris(chloromethyl)phosphine oxide and methylbis(chloromethyl)phosphine oxide were unexpectedly found to be solublein water and in aqueous alkali, and for this reason could be applied tocellulosic materials from a single bath. The bromoand iodo-phosphineoxides are insoluble in water or in aqueous alkali. They can beconveniently applied from miscible organic solvent in which thephosphine oxides are soluble. Dimethylformamide is a particularlysuitable solvent for the compounds of this invention. It is preferablethat water be present in the solutions of the phosphine oxides so thatpenetration into cellulosic fibers can be achieved. When a combinationof water and an organic solvent is used it is necessary to carry out theapplication to cellulose in two steps. The aqueous alkali may be appliedto the cellulose first, followed by the solution of the phosphine oxide,or the phosphine oxide may be applied first followed by the aqueousalkali.

The application of the water soluble phosphine oxides to cotton fabricmay be carried out as follows: The cotton fabric is then impregnatedwith the solution, the fabric dried and cured at temperatures rangingabout from to C. for about from 5 to 30 minutes of time.

The application of the water insoluble phosphine oxides to cotton fabricmay be carried out as follows: The phosphine oxide is dissolved in asuitable water-miscible organic solvent, and water added in a quantitysuch that precipitation of the phosphine oxide does not occur. Thefabric is then impregnated with the solution, dried, and cured attemperatures about from 110 to 150 C. for about from 5 to 30 minutes oftime, the longer times are required for the lower temperatures.

Any alkali hydroxide or alkali carbonate is a suitable catalyst for thereaction of the bisand tris(haloalkyl) phosphine oxides of the instantinvention with cellulosic textiles. Sodium carbonate or sodium hydroxideare preferred catalysts. Catalyst concentrations may be varied aboutfrom 0.5% to 10%.

The cellulosic textile can be impregnated and heated by any apparatusconventionally used for processing such materials.

Restating the invention, it can be described in general as a process forimparting wet wrinkle resistance to cotton and other cellulosic textilescomprising:

(a) impregnating a cotton or other cellulosic textile with a solutioncontaining about from 0.5% to 10% of an alkali catalyst selected fromthe group consisting of sodium hydroxide and sodium carbonate, and aboutfrom 5% to 10% of a haloalkylphosphine oxide selected from the groupconsisting of tris(chloromethyDphosphine oxide,tris(bromomethyl)phosphine oxide, tris- (iodomethyl)phosphine oxide,methyl bis(chloromethyl) phosphine oxide, methylbis(bromomethyl)phosphine oxide, and methyl bis(iodomethyDphosphineoxide,

(b) drying the wet, impregnated textile for about 5 minutes of time atabout 85 C., and

(c) curing the dried impregnated textile for about from to 30 minutes oftime at about from 110 to 150 C., using the longer periods of time withthe lower temperatures.

The following examples illustrate the methods of carrying out theinvention, and are included for purposes of illustration, not as alimitation thereof. Wrinkle recovery tests were carried out by theMonsanto method, ASTM designation D142459. All percentages and parts inthe examples are by weight.

EXAMPLE 1 Eight solutions were prepared by dissolvingtris(chloromethyl)phosphine oxide in aqueous sodium hydroxide of theconcentrations indicated in Table I. External cooling was employed whennecessary to prevent the solution from heating up spontaneously. Eachsolution contained of the phosphine oxide. Fabric samples wereimpregnated with the solutions, dried for 5 minutes at 85 C., and curedin an oven for 5 minutes at 150 C. or minutes at 110 C. The samples werethen washed free of alkali, and submitted to wet wrinkle recovery tests,and phosphorus and chlorine analyses. The results obtained are shown inTable I. Highest phosphorus and chlorine content, and wet wrinklerecovery values were obtained at 10% NaOH concentration. Fibers from allof the samples were found insoluble in 0.5 molar cupriethylenediaminehydroxide (Cuene).

TABLE 1 NaOII Curing Phos- Wet wrinkle concn., temp., phorus, Chlorine,recovery angle, percent percent percent degrees 110 0. 17 0. 34 185Control. 1G4

EXAMPLE 2 Fabric samples were treated in exactly the same way as inExample 1 except that methyl bis(chloromethyl) phosphine oxide was used.Fabric and other data are shown in Table II.

All fabric samples were insolubles in Cuene, contained phosphorus andchlorine, and had improved wet wrinkle recovery over the control.

EXAMPLE 3 Tris(bromomethyl)phosphine oxide (5.0 grams) was dissolved in22.5 grams of dimethyl formamide. Water (22.5 grams) was added. Fivesamples of cotton printcloth were impregnated with the solution anddried for 5 minutes at 85 C. Each sample was then impregnated with adilferent concentration of aqueous sodium hydroxide, again dried for 5minutes at 85 C., and cured for 5 minutes at 150 C. Fabric and otherdata are shown in Table III.

TABLE III Wet wrinkle Phosphorus, Bromine, recovery angle, NaOH percentpercent egrees 0. 15 0. 09 106 0. l4 0. 04 195 0. 11 0.03 180 0. 0!) 0.02 204 0. 18 0.26 221 Control 164 All of the samples were insoluble inCuene.

EXAMPLE 4 Methyl bis(iodomethyl)phosphine oxide (5.0 grams) wasdissolved in 22.5 grams of dimethyl formamide at 70 C. Water (22.5grams) was added while holding the temperature at about 70 C. Sixsamples of cotton printcloth were impregnated with the hot solution anddried for 5 minutes at C. Each sample was then impregnated with adifferent concentration of aqueous sodium hydroxide, again dried for 5minutes at 85 C., and cured for 5 minutes at 150 C. Fabric and otherdata are shown in Table IV.

A number of samples of cotton printcloth were treated with methylbis(chloromethyl)phosphine oxide as in Example 2 except that sodiumcarbonate solutions were used instead of the sodium hydroxide solutions.Crosslinking was observed as present in the treated samples whendetermined by their insolubility in the Cuene.

EXAMPLE 6 A sample of printcloth was treated withtris(bromomethyl)phosphine oxide as in Example 3 except that a 10%sodium carbonate solution was used instead of 10% sodium hydroxidesolution. The fibers were insoluble in the Cuene. The fabric contained0.12% phosphorus and 0.23% bromine.

We claim:

1. A process for imparting wet wrinkle resistance to a cellulosictextile comprising (a) impregnating the cellulosic textile with asolution containing about from 0.5% to 10% of an alkali catalystselected from the group consisting of sodium hydroxide and sodiumcarbonate, and about from 5% to 10% of a haloalkylphosphine oxideselected from the group consisting of tris(chloromethyl)phosphine oxide,tris(bromornethyl)phosphine oxide, tris (iodomethyl)phosphine oxide,methyl bis(chloromethyl)phosphine oxide, methyl bis(bromomethyl)phosphine oxide, and methyl bis(iodomethyl)ph0sphine oxide,

(b) drying the wet, impregnated textile for about 5 minutes of time atabout 85 C., and

(c) curing the dried, impregnated textile for about from 5 to 30 minutesof time at about from 110 to C., using the longer periods of time withthe lower temperatures.

2. A process for imparting wet wrinkle resistance to a cellulosictextile comprising (a) impregnating the cellulosic textile with anaqueous solution containing about from 2.5% to 10% of an alkali catalystselected from the group consisting of sodium hydroxide and sodiumcarbonate, and about from to of a haloalkylphosphine oxide selected fromthe group consisting of tris(chloromethyl)phosphine oxide, and methylbis(chloromethyl)phosphine oxide,

(b) drying the wet, impregnated textile for about 5 minutes of time atabout 85 C., and

(c) curing the dried, impregnated textile for about from 5 to 30 minutesof time at about from 110 to 150 C., using the longer periods of timewith the lower temperatures.

3. The process of claim 2 wherein the alkali catalyst is sodiumhydroxide and the haloalkylphosphine oxide istris(chloromethyl)phosphine oxide.

4. The process of claim 2 wherein the alkali catalyst is sodiumhydroxide and the haloalkylphosphine oxide is methylbis(chloromethyl)phosphine oxide.

5. The process of claim 2 wherein the alkali catalyst is sodiumcarbonate and the haloalkylphosphine oxide is tris (chloromethyl)phosphine oxide.

6. The process of claim 2 wherein the alkali catalyst is sodiumcarbonate and the haloalkylphosphine oxide is methylbis(chloromethyl)phosphine oxide.

7. A process for imparting wet wrinkle resistance to a cellulosictextile comprising (a) impregnating the cellulosic textile with anaqueous solution containing about from 1.5% to 10% of an alkali catalystselected from the group consisting of sodium hydroxide and sodiumcarbonate,

(b) drying the wet, impregnated textile for about 5 minutes of time atabout 85 C.,

(c) impregnating the dried textile from step (b) with a 50% aqueousdimethylformamide solution containing about from 5% to 10% of ahaloalkylphosphine oxide selected from the group consisting oftris(bromomethyl)phosphine oxide, and methyl his (bromomethyl)phosphineoxide,

(d) drying the reimpregnated textile from step (c) for about 5 minutesof time at about 85 C., and

(e) curing the twice-impregnated, twice-dried textile for about from 5to 30 minutes of time at about from 110 to 150 C., using the longerperiods of time with the lower temperatures.

8. The process of claim 7 wherein the alkali catalyst is sodiumhydroxide and the haloalkylphosphine oxide is tris(bromomethyl)phosphine oxide.

9. The process of claim 7 wherein the alkali catalyst is sodiumhydroxide and the haloalkylphosphine oxide is methylbis(bromomethyl)phosphine oxide.

10. The process of claimv 7 wherein the alkali catalyst is sodiumcarbonate and the haloalkylphosphine oxide is tris(bromomethyl)phosphineoxide.

11. The process of claim 7 wherein the alkali catalyst is sodiumcarbonate and the haloalkylphosphine oxide is methylbis(bromomethyl)phosphine oxide.

12. A process for imparting wet wrinkle resistance to a cellulosictextile comprising (a) impregnating the cellulosic textile with anaqueous solution containing about from 0.5 to 10% of an alkali catalystselected from the group consisting of sodium hydroxide and sodiumcarbonate,

(b) drying the wet, impregnated textile for about 5 minutes of time atabout 85 C.,

(c) impregnating the dried textile from step (b) with a 50% aqueousdimethylformamide solution at 70 C. containing about from 5% to 10% of ahaloalkylphosphine oxide selected from the group consisting oftris(iodomethyl)phosphine oxide, and methyl bis (iodomethyl)phosphineoxide,

(d) drying the reimpregnated textile from step (c) for about 5 minutesof time at about 85 C., and

(e) curing the twice-impregnated, twice-dried textile for about from 5to 30 minutes of time at about from 110 to 150 C., using the longerperiods of time with the lower temperatures.

13. The process of claim 12 wherein the alkali catalyst is sodiumhydroxide and the haloalkylphosphine oxide is tris(iodomethyl)phosphineoxide.

14. The process of claim 12 wherein the alkali catalyst is sodiumhydroxide and the haloalkylphosphine oxide is methyl bis(iodomethyl)phosphine oxide.

15. The process of claim 12 wherein the alkali catalyst is sodiumcarbonate and the haloalkylphosphine oxide is tris(iodomethyl)phosphineoxide.

16. The process of claim 12 wherein the alkali catalyst is sodiumcarbonate and the haloalkylphosphine oxide is methylbis(iodomethyl)phosphine oxide.

17. A process for imparting wet wrinkle resistance to a cellulosictextile comprising (a) impregnating the cellulosic textile with a 50%aqueous dimethylformamide solution containing about from 5% to 10% of ahaloalkylphosphine oxide selected from the group consisting of tris(bromomethyl)phosphine oxide, and methyl bis (bromomethyl) phosphineoxide,

(b) drying the wet, impregnated textile for about 5 minutes of time atabout C.,

(c) impregnating the dried textile from step (b) with an aqueoussolution containing about from 1.5% to 10% of an alkali catalystselected from the group consisting of sodium hydroxide and sodiumcarbonate,

(d) drying the reimpregnated textile from step (c) for about 5 minutesof time at about 85 C., and

(e) curing the twice-impregnated, twice-dried textile for about from 5to 30 minutes of time at about from to C., using the longer periods oftime with the lower temperatures.

18. The process of claim 17 wherein the alkali catalyst is sodiumhydroxide and the haloalkylphosphine oxide is tris bromomethyl phosphineoxide.

19. The process of claim 17 wherein the alkali catalyst is sodiumhydroxide and the haloalkylphosphine oxide is methylbis(bromomethyl)phosphine oxide.

20. The process of claim 17 wherein the alkali catalyst is sodiumcarbonate and the haloalkylphosphine oxide is tris (bromomethyl)phosphine oxide.

21. The process of claim 17 wherein the alkali catalyst is sodiumcarbonate and the haloalkylphosphine oxide is methylbis(bromomethyl)phosphine oxide.

22. A process for imparting wet wrinkle resistance to a cellulosictextile comprising (a) impregnating the cellulosic textile with a 50%aqueous dimethylformamide solution at 70 C. containing about from 5% to10% of a haloalkylphosphine oxide selected from the group consisting oftris(iodomethyl)phosphine oxide, and methyl bis (iodomethyl) phosphineoxide,

(b) drying the wet, impregnated textile for about 5 minutes of time atabout 85 C.,

(c) impregnating the dried textile from step (b) with an aqueoussolution containing about from 0.5% to 10% of an alkali catalystselected from the group consisting of sodium hydroxide and sodiumcarbonate,

(d) drying the reimpregnated textile from step (c) for about 5 minutesof time at about 85 C., and

(e) curing the twice-impregnated, twice-dried textile for about from 5to 30 minutes of time at about from 110 to 150 C., using the longerperiods of time with the lower temperatures.

23. The process of claim 22 wherein the alkali catalyst is sodiumhydroxide and the haloalkylphosphine oxide is tris(iodomethyl)phosphineoxide.

24. The process of claim 22 wherein the alkali catalyst is sodiumhydroxide and the haloalkylphosphine oxide is methylbis(iodomethyl)phosphine oxide.

25. The process of claim 22 wherein the alkali catalyst is sodiumcarbonate and the haloalkylphosphine oxide is tris (iodomethyl)phosphineoxide.

is sodium carbonate and the haloalkylphosphine oxide is methylbis(iodomethyl)phosphine oxide.

References Cited UNITED STATES PATENTS Van Gorder et a1. 8-120 Dock FonToy et a1. 8-116 'Reeves et a1. 8116 Drake et a1. 8--120 1 Goldstein eta1. 8-116 7 26. The process of claim 22 wherein the alkali catalyst 8FOREIGN PATENTS 893,283 4/1962 Great Britain.

OTHER REFERENCES 5 Drake et al., Textile Research Journal, vol. 29, pp.

